Heretofore, telechelic polymers made from dienes had various shortcomings or limitations arising from the polymerization process such as high solution viscosity, high bulk viscosity, high vinyl content which increased with lower molecular weight of the telechelic polymer, and the like. Often, gelation occurred. Such telechelic polymers were generally prepared utilizing only an organopolylithium initiator and a polar solvent to facilitate dissolution.
U.S. Pat. No. 3,278,508, to Kahle et al. relates to the polymerization of conjugated dienes such as 1,3-isoprene to form rubbery polymers having a high percentage of cis-1,4-addition product and reduced solution viscosities utilizing an initiator of an organolithium in combination with an organoaluminum compound for producing high molecular weight polymers.
U.S. Pat. No. 3,321,487, to P. Chini et al. relates to organo-aluminum compounds derived from acetylene.
U.S. Pat. No. 3,388,178, to C. Kamienski et al. relates to preparation of lithium-conjugated polyene hydrocarbon adducts by providing a mixture containing (a) a dispersion of finely divided lithium in an inert liquid, (b) a volatile liquid aromatic hydrocarbon, and (c) an inert liquid ether, gradually adding a conjugated polyene hydrocarbon while maintaining the reaction mixture at a low temperature, preferably below 0.degree. C., said reaction being advantageously carried out in the presence of a catalyst in the form of a lithium-conjugated polyene hydrocarbon adduct added to the reaction mixture in the form of a solution in a volatile liquid aromatic hydrocarbon, passing an inert gas over the reaction product mixture to purge the same of the ether, then adding an additional quantity of a volatile liquid hydrocarbon and warming the reaction product mixture, and then filtering to remove unreacted lithium metal whereby to produce a clear solution of the lithium-conjugated polyene hydrocarbon adduct in said volatile liquid hydrocarbon.
U.S. Pat. No. 3,578,642, to F. Mueller et al. relates to alkene oxides which are polymerized alone or copolymerized with acrylic acid esters, methacrylic acid esters, lactones, or other alkene oxides in the presence of an organoalkaline earth compound and an organoaluminum compound.
U.S. Pat. No. 3,629,213, to A. Onishi et al. relates to conjugated diene polymers having a desirable microstructure for a rubbery elastomer produced by contacting at least one conjugated diene or a mixture of a conjugated diene with a vinyl-substituted aromatic hydrocarbon with a catalyst consisting of an organolithium compound and a barium compound. In the polymers of at least one conjugated diene, the polymers having a low content of 1,2- or 3,4-structure and a high trans-1,4-structure in conjugated diene unit can be obtained by adjusting the ratio of the catalyst components and in the copolymers of a conjugated diene and a vinyl-substituted aromatic hydrocarbon.
U.S. Pat. No. 3,664,989, to Petrov et al. relates to a method of preparing a homopolymer or a copolymer having terminal functional groups from a conjugated diene or optionally with a styrene type monomer having a pre-set molecular weight wherein the polymerization is carried out in the presence of an alkali metal catalyst such as lithium, and a modifier obtained by reacting an alkali metal with a conjugated hydrocarbon and an organoaluminum compound.
U.S. Pat. No. 3,725,301, to Mueller et al. relates to a polymerization initiator formed on admixing an organoalkaline earth compound and an organoaluminum compound, wherein the organoalkaline earth compound is the reaction product of an alkaline earth metal with a pyridine-type compound, polynuclear aromatic compound, or polyaryl-substituted ethylenic compound.
U.S. Pat. No. 3,862,100, to Halasa et al. relates to alkali metal aliphatic and aromatic hydrocarbon acetals and ketals which are initiators for the polymerization of conjugated dienes and copolymerization of conjugated diene and vinyl monomers. Mono-acetal and mono-ketal polymers are produced by termination of the foregoing polymers and copolymers with methanol, isopropanol, etc., diacetal and diketal polymers are produced by terminating said polymers and copolymers with a joining agent, e.g., Cl.sub.2 Si(CH.sub.3).sub.2, and polyacetal and polyketal polymers and copolymers are produced by terminating said polymers and copolymers with a polyfunctional joining agent, e.g., Cl.sub.3 SICH.sub.3. Other mono-acetal and mono-ketal polymers are prepared by terminating said polymers and copolymers with ethylene oxide or carbon dioxide. The terminally reactive acetal polymers can be converted to other polymeric products.
U.S. Pat. No. 3,899,474, to Goldenberg et al. relates to conjugated diolefins which are first converted to polymers in the presence of specific derivatives of transition metal carboxylates, for example an etherate of trifluoracetato nickel halide. The crude polymer containing catalyst residues is admixed with a reducing metal compound, for example triethylaluminum, and a hydrogen pressure is applied thereto. The final product is a partially or totally hydrogenated polymer. Specific hydrogenated butadiene polymers may be obtained therefrom.
U.S. Pat. No. 4,041,988, to Bach et al. relates to a recirculation process and apparatus for the preparation of normally liquid telomers derived from the reaction of a gaseous taxogen with a solution in a liquid telogen, such as toluene, of an organometal telomerization initiator, such as a mixture or complex of n-butyllithium and potassium t-butoxide, in a container, wherein a controlled stream of the gaseous taxogen is continuously passed through fine apertures, as in a screen, into the liquid telogen solution of said initiator while said telogen solution is passed from said container through a reaction zone in a reaction chamber, whereby to produce the normally liquid telomer, and, thereafter, said liquid telomer is continuously returned to co-mingle with the solution in the container of said telogen and initiator, and continuously recirculating the contents of said container into said reaction zone for further reaction with said gaseous taxogen until the desired concentration of liquid telomer is produced.
U.S. Pat. No. 4,049,732, to Bach et al. relates to a continuous process and apparatus for the preparation of normally liquid telomers derived from the reaction of a liquid telogen, such as toluene, with a polymerizable monomeric taxogen in gaseous form, such as 1,3-butadiene monomer, in the presence of an organometal telomerization initiator, such as a mixture or complex of n-butyllithium and potassium t-butoxide, wherein a controlled stream of the gaseous taxogen is continuously passed through fine apertures, as in a screen, into the liquid telogen containing said initiator disposed in a reaction zone in a reaction chamber, whereby to produce the normally liquid telomer, and, thereafter said telomer is continuously passed through a conduit into an additional reaction zone or zones and reacted in similar manner with additional gaseous taxogen until the desired concentration of liquid telomer is produced. The process is most desirably carried out in a controlled manner to prevent any undesirable excess of the taxogen from accumulating during the chain transfer step of the telomerization process.
U.S. Pat. No. 4,092,268, to deZarauz relates to polymers of conjugated dienes and copolymers of conjugated dienes with vinyl aromatic compounds or with other conjugated dienes having a high content of trans-1,4 linkages and a low content of 1,2 or 3,4 linkages and an elastomeric character are prepared by use of a catalytic composition which comprises (a) an organolithium initiator and (b) a co-catalyst system comprising a compound of barium or strontium and an organometallic compound of a metal of Group IIB or IIIA of the Mendeleev periodic table of elements.
U.S. Pat. No. 4,518,753, to Richards et al. relates to a process for the anionic polymerization of a conjugated diene in the presence of RLi and a hindered triaryl boron or aluminum derivatives.
British Patent No. 1,294,890, to Petrov et al. relates to the production of hydrocarbon polymers containing functional end groups by treating a conjugated diene polymer containing at the chain ends thereof organometallic groups of a metal of Group II or Group III of the Periodic Table but excluding a transitional metal, with a reagent selected from an alkylene oxide, carbon dioxide, oxygen, sulfur, and epichlorohydrin.
An article, "Synthesis and Characterization of Functional Diene Oligomers in View of Their Practical Applications," Die Angewandte Makromolekulare Chemie, 70. (1978)9-30 (Nr. 1032), relates to the utilization of various initiators for butadiene oligomerization.
An article, "Functionally Terminal Polymers via Anionic Methods," Schulz, Sanda and Willoughby, Chapter 27, Anionic Polymerization, Kinetics, Mechanisms and Synthesis, Symposium Series No. 166, American Chemical Society, Washington, D.C., 1981, relates to reacting monoacetal polybutadienyl lithium with ethylene oxide or carbon dioxide. Dihydroxy or hydroxy-carboxy terminated polymers are produced.